{
  "abstract": "Dimethyl carbonate (DMC)-based electrolytes consistently show higher ionic conductivity than diethyl carbonate (DEC)-based ones despite their comparable viscosities and dielectric constants. Here, classical MD simulations with LiPF 6 as the salt are used to elucidate the molecular origins of this difference. LiPF 6 -DMC electrolytes contain a larger population of solvent-separated ion pairs (SSIPs), whereas LiPF 6 -DEC electrolytes exhibit a higher population of ion aggregates (AGGs). Among various species, SSIPs make the dominant contribution to ionic conductivity, accounting for the higher conductivity of DMC-based electrolytes. Both solvents exist predominantly in two conformations, cis-cis (CC) and cis-trans (CT), defined by the torsional angle about the C-O bond; the former is largely non-polar, while the latter has a substantial dipole moment of nearly 4 D. In both electrolytes, the CT fraction increases with salt concentration, consistent with the stronger ion-dipole interactions of the CT conformer with ions and the fractions are comparable for DMC and DEC. Nevertheless, DMC retains a larger fraction of lithium ions as SSIPs. Although CT-DMC and CT-DEC have nearly identical polarities, more CT-DMC molecules coordinate Li + than CT-DEC molecules do. This difference arises from their distinct conformational sizes: CT-DMC has a volume approximately 8% smaller than that of CC-DMC, whereas the corresponding decrease for DEC is only about 2%. The smaller relative size of CT-DMC permits more of it to coordinate Li + to yield effective electrostatic shielding. This, in turn, leads to a larger SSIP population and higher ionic conductivity of LiPF 6 -DMC relative to LiPF 6 -DEC.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 2,
  "authors": [
    {
      "name": "Mansi Jain",
      "orcid": "0009-0000-6760-0391"
    },
    {
      "name": "Sundaram Balasubramanian",
      "orcid": "0000-0002-3355-6764"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/5bmf1zz9bdff8.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15009516/v1",
  "fulltext_url": null,
  "id": "5bmf1zz9bdff8",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009516/v1",
  "language": null,
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "2208|Advanced Battery Materials and Technologies"
    ]
  ],
  "openalex": "W7214611367",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15009516/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-28",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/5bmf1zz9bdff8.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:21Z",
      "native_id": "10.26434/chemrxiv.15009516",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009516/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "source:chemrxiv",
      "subfield": "general"
    }
  ],
  "title": "Deciphering Ionic Conductivity Differences in Linear Carbonate Electrolytes: Conformational Shrinkage and Solvation Structure in Dimethyl vs Diethyl Carbonate",
  "title_text": "Deciphering Ionic Conductivity Differences in Linear Carbonate Electrolytes: Conformational Shrinkage and Solvation Structure in Dimethyl vs Diethyl Carbonate",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:21Z",
  "url": "https://research.draconitic.com/paper/5bmf1zz9bdff8",
  "venue": "ChemRxiv",
  "versions": []
}